U.S. patent number 10,829,639 [Application Number 15/773,589] was granted by the patent office on 2020-11-10 for curable organopolysiloxane composition and cured product thereof.
This patent grant is currently assigned to Dow Toray Co., Ltd.. The grantee listed for this patent is Dow Corning Toray Co., Ltd.. Invention is credited to Takuya Ogawa, Satoshi Onodera.
United States Patent |
10,829,639 |
Ogawa , et al. |
November 10, 2020 |
Curable organopolysiloxane composition and cured product
thereof
Abstract
A curable organopolysiloxane composition comprises: (A) an
alkenyl group-containing organopolysiloxane; (B) a compound having
at least two thiol groups in a molecule; (C) an azo compound and/or
an organic peroxide; and (D) at least one type of compound selected
from the group consisting of quinone compounds, compounds having
one or two aromatic hydroxyl groups in a molecule, compounds having
one thiol group in a molecule, nitrosamine compounds, hydroxylamine
compounds, and phenothiazine compounds. The curable
organopolysiloxane composition can be quickly cured even at a
relatively low temperature (e.g. of 80.degree. C. or lower) to form
a cured film with excellent adhesion to an object to be coated.
Inventors: |
Ogawa; Takuya (Chiba,
JP), Onodera; Satoshi (Chiba, JP) |
Applicant: |
Name |
City |
State |
Country |
Type |
Dow Corning Toray Co., Ltd. |
Tokyo |
N/A |
JP |
|
|
Assignee: |
Dow Toray Co., Ltd. (Tokyo,
JP)
|
Family
ID: |
1000005172242 |
Appl.
No.: |
15/773,589 |
Filed: |
November 4, 2016 |
PCT
Filed: |
November 04, 2016 |
PCT No.: |
PCT/JP2016/082889 |
371(c)(1),(2),(4) Date: |
May 04, 2018 |
PCT
Pub. No.: |
WO2017/082180 |
PCT
Pub. Date: |
May 18, 2017 |
Prior Publication Data
|
|
|
|
Document
Identifier |
Publication Date |
|
US 20180327594 A1 |
Nov 15, 2018 |
|
Foreign Application Priority Data
|
|
|
|
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Nov 13, 2015 [JP] |
|
|
2015-223521 |
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08G
77/28 (20130101); C09D 183/06 (20130101); C08K
5/23 (20130101); C08L 83/04 (20130101); C08K
5/14 (20130101); C09D 183/04 (20130101); C08K
5/37 (20130101); C08K 5/08 (20130101); C09D
183/04 (20130101); C08L 83/00 (20130101); C08K
5/14 (20130101); C08K 5/23 (20130101); C08K
5/04 (20130101); C09D 183/04 (20130101); C08L
83/00 (20130101); C08K 5/14 (20130101); C08K
5/23 (20130101); C08K 5/08 (20130101); C09D
183/04 (20130101); C08L 83/00 (20130101); C08K
5/14 (20130101); C08K 5/23 (20130101); C08K
5/46 (20130101); C09D 183/04 (20130101); C08L
83/00 (20130101); C08K 5/14 (20130101); C08K
5/23 (20130101); C08K 5/37 (20130101) |
Current International
Class: |
C08K
5/23 (20060101); C09D 183/04 (20060101); C08G
77/28 (20060101); C08L 83/04 (20060101); C08K
5/14 (20060101); C09D 183/06 (20060101); C08K
5/37 (20060101); C08K 5/08 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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101965542 |
|
Feb 2011 |
|
CN |
|
103874736 |
|
Jun 2014 |
|
CN |
|
0492830 |
|
Jul 1996 |
|
EP |
|
H03227365 |
|
Oct 1991 |
|
JP |
|
2008184514 |
|
Aug 2008 |
|
JP |
|
2009086291 |
|
Apr 2009 |
|
JP |
|
2013043902 |
|
Mar 2013 |
|
JP |
|
2015096559 |
|
May 2015 |
|
JP |
|
2015193820 |
|
Nov 2015 |
|
JP |
|
2016060783 |
|
Apr 2016 |
|
JP |
|
2015069454 |
|
May 2015 |
|
WO |
|
2017068762 |
|
Apr 2017 |
|
WO |
|
Other References
Data sheet from Akzo Nobel "Initiators for High Polymers", 17
pages, 2006. (Year: 2006). cited by examiner .
Azo Polymerization Initiators Comprehensive Catalog from Wako Pure
Chemical Industries, Ltd. 36 pages, 2016. (Year: 2016). cited by
examiner .
Sigma Aldrich data sheet for Free Radical Initiators, 2 pages, 1999
(Year: 1999). cited by examiner .
PCT/JP2016/082889 International Search Report dated Dec. 13, 2016,
4 pages. cited by applicant .
English language abstract and machine translation for JP2008184514
(A) extracted from http://worldwide.espacenet.com database on May
17, 2018, 39 pages. cited by applicant .
English language abstract and machine translation for JP2009086291
(A) extracted from http://worldwide.espacenet.com database on Jun.
7, 2018, 47 pages. cited by applicant .
English language abstract and machine translation for JP2013043902
(A) extracted from http://worldwide.espacenet.com database on Jun.
7, 2018, 43 pages. cited by applicant .
English language abstract and machine translation for JP2015096559
(A) extracted from http://worldwide.espacenet.com database on Jun.
7, 2018, 20 pages. cited by applicant .
English language abstract and machine translation for JP2015193820
(A) extracted from http://worldwide.espacenet.com database on May
17, 2018, 35 pages. cited by applicant .
Machine assisted English translation of CN101965542A obtained from
https://patents.google.com/patent dated Jul. 17, 2020, 25 pages.
cited by applicant .
Machine assisted English translation of JP2016060783A obtained from
https://worldwide.espacenet.com/ dated Aug. 20, 2020, 14 pages.
cited by applicant.
|
Primary Examiner: Loewe; Robert S
Attorney, Agent or Firm: Warner Norcross + Judd LLP
Claims
The invention claimed is:
1. A curable organopolysiloxane composition comprising: (A) an
alkenyl group-containing organopolysiloxane of the following
average compositional formula:
R.sup.1.sub.aR.sup.2.sub.bSiO.sub.(4-a-b)/2 wherein R.sup.1
represents a C.sub.2-12 alkenyl group; R.sup.2 represents a
hydrogen atom, C.sub.1-12 alkyl group, C.sub.6-20 aryl group,
C.sub.7-20 aralkyl group, hydroxyl group, or C.sub.1-6 alkoxy
group; there are at least two R.sup.1 in a molecule; and "a" and
"b" are numbers satisfying: 0<a.ltoreq.1, 0<b<3, and
0.8<a+b<3; (B) a compound having at least two thiol groups in
a molecule, in an amount such that the thiol groups in component
(B) is 0.3 to 3 mol with respect to 1 mol of the alkenyl groups in
component (A); (C) an azo compound with a 10 hour half-life
temperature of 25.degree. C. or higher but lower than 60.degree.
C.; and (D) at least one type of compound selected from the group
consisting of quinone compounds, compounds having one or two
aromatic hydroxyl groups in a molecule, compounds having one thiol
group in a molecule, nitrosamine compounds, hydroxylamine
compounds, and phenothiazine compounds.
2. The curable organopolysiloxane composition according to claim 1,
wherein component (A) comprises the C.sub.6-20 aryl groups.
3. The curable organopolysiloxane composition according to claim 1,
wherein component (B) comprises: (B1) a thiol group-containing
organopolysiloxane of the following average compositional formula:
R.sup.3.sub.cR.sup.4.sub.dSiO.sub.(4c-d)/2 wherein R.sup.3 is at
least one type of thiol group selected from the group consisting of
thiolalkyl groups and thiolaryl groups; R.sup.4 represents a
hydrogen atom, C.sub.1-12 alkyl group, C.sub.6-20 aryl group,
C.sub.7-20 aralkyl group, hydroxyl group, or C.sub.1-6 alkoxy
group; there are at least two R.sup.3 in a molecule; and "c" and
"d" are numbers satisfying: 0<c<1, 0<d<3, and
0.8<c+d<3; and/or (B2) a thiol compound having at least two
thiol groups in a molecule.
4. The curable organopolysiloxane composition according to claim 1,
wherein the content of component (C) is in the range of 0.01 to 10
mass % with respect to the total amount of components (A) to
(D).
5. The curable organopolysiloxane composition according to claim 1,
wherein the content of component (D) is in the range of 0.001 to 10
mass % with respect to the total amount of components (A) to
(D).
6. The curable organopolysiloxane composition according to claim 1,
further comprising (E) an organic solvent.
7. The curable organopolysiloxane composition according to claim 6,
wherein the content of component (E) is no greater than 3,000 parts
by mass with respect to 100 parts by mass of the total amount of
components (A) to (D).
8. The curable organopolysiloxane composition according to claim 1,
further defined as a coating composition.
9. A cured product obtained by curing the curable
organopolysiloxane composition according to claim 1.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is the National Stage of International Application
No. PCT/JP2016/082889 filed on 04 Nov. 2016, which claims priority
to and all advantages of Japanese Patent Appl. No. 2015-22352 filed
on 13 Nov. 2015, the content of which is hereby incorporated by
reference.
TECHNICAL FIELD
The present invention relates to a curable organopolysiloxane
composition and a cured product thereof.
BACKGROUND ART
Curable organopolysiloxane compositions are used for adhesives,
sealants, coating agents, and the like of electric/electronic parts
because they can be cured to form cured products with excellent
adhesion, bonding property, weather resistnce, and electrical
characteristics. Well-known curing reactions for such compositions
include dehydration condensation reaction, dealcoholization
condensation reaction, and other condensation reaction type curing;
hydrosilylation reaction of ethylenic unsaturated groups and
silicon atom-bonded hydrogen atoms, ene-thiol reaction of
ethyleneic unsaturated groups and mercapto groups, and other
addition reactions. Addition reaction type compositions are usually
used in the coating applications since it is difficult for gapes or
cracks to occur during curing and warping after curing can be
suppressed.
For example, Patent Document 1 discloses a sealant for a liquid
crystalline comprising: a radical curable resin having two or more
ethylenic unsaturated bonds in a molecule; a thiol compound having
two or more primary or secondary mercapto groups in a molecule and
having a tertiary or quarternary carbon as the carbon at
.beta.-position with respect to said primary mercapto group; and a
radical polymerization initiator. While, Patent Document 2
discloses a curable resin composition comprising: a mercapto
group-containing polysiloxane; and a vinyl-based compound.
These compositions, however, substantially require heating at a
temperature of 110.degree. C. or higher during the curing process.
It is necessary to increase the activity of the polymerization
initiator at a low temperature of about 80.degree. C. in order to
complete the curing reaction quickly at that temperature. As a
result, however, it becomes difficult to maintain a good storage
stability at ordinary temperature.
Therefore, it is required to develop an addition reaction type
curable organopolysiloxane composition with good storage stability
at ordinary temperature so that it can have sufficient workability,
while it can be quickly cured at a low temperature of about
80.degree. C.
CITATION LIST
Patent Literature
Patent Document 1: Japanese Unexamined Patent Application
Publication No. 2009-86291
Patent Document 2: Japanese Unexamined Patent Application
Publication No. 2013-43902
SUMMARY OF INVENTION
Technical Problem
An objective of the present invention is to provide a curable
organopolysiloxane composition, which can be quickly cured even at
a relatively low temperature of 80.degree. C. or lower to form a
cured film with excellent adhesion to an object to be coated, and a
cured product with excellent adhesion to the object.
Solution to Problem
The curable organopolysiloxane composition of the present invention
is characterized by comprising:
(A) an alkenyl group-containing organopolysiloxane represented by
the following average compositional formula:
R.sup.1.sub.aR.sup.2.sub.bSiO.sub.(4-a-b)/2
wherein, R.sup.1 represents a C.sub.2-12 alkenyl group; R.sup.2
represents a hydrogen atom, C.sub.1-12 alkyl group, C.sub.6-20 aryl
group, C.sub.7-20 aralkyl group, hydroxyl group, or a C.sub.1-6
alkoxy group; however, there are at least two R.sup.1 in a
molecule; "a" and "b" are numbers satisfying: 0<a.ltoreq.1,
0<b<3, and 0.8<a+b<3;
(B) a compound having at least two thiol groups in a molecule, in
an amount such that the thiol groups in component (B) is 0.3 to 3
mol with respect to 1 mol of the alkenyl groups in component
(A);
(C) an azo compound and/or an organic peroxide; and
(D) at least one type of compound selected from a group consisting
of quinone compounds, compounds having one or two aromatic hydroxyl
groups in a molecule, compounds having one thiol group in a
molecule, nitrosamine compounds, hydroxylamine compounds, and
phenothiazine compounds.
The cured product of the present invention is characterized by
being obtained by curing the aforementioned curable
organopolysiloxane composition.
Effects of Invention
The curable organopolysiloxane composition of the present invention
has good curability at relatively low temperature and can form
cured film with excellent adhesion to an object to be coated. The
cured product of the present invention is characterized by having
excellent adhesion to the object.
DETAILED DESCRIPTION OF THE INVENTION
First, the curable organopolysiloxane composition of the present
invention will be described in details.
The alkenyl group-containing organopolysiloxane for component (A)
is a main component of this composition and is represented by the
following average compositional formula:
R.sup.1.sub.aR.sup.2.sub.bSiO.sub.(4-a-b)/2
In the formula, R.sup.1 represents a C.sub.2-12 alkenyl group, such
as vinyl group, allyl group, butenyl group, pentenyl group, hexenyl
group, heptenyl group, octenyl group, nonenyl group, decenyl group,
undecenyl group, and dodecenyl group. In consideration of economy
and reactivity, it is preferably vinyl group, allyl group, hexenyl
group, or octenyl group. Component (A) has at least two alkenyl
groups in a molecule.
In the formula, R.sup.2 represents a hydrogen atom, C.sub.1-12
alkyl group, C.sub.6-20 aryl group, C.sub.7-20 aralkyl group,
hydroxyl group, or a C.sub.1-6 alkoxy group. Examples of the alkyl
group include methyl group, ethyl group, propyl group, butyl group,
pentyl group, hexyl group, heptyl group, octyl group, nonyl group,
decyl group, undecyl group, and dodecyl group. Methyl group is
preferred in consideration of economy and heat resistance. Examples
of the aryl group include phenyl group, tolyl group, xylyl group,
naphthyl group, biphenyl group, and phenoxyphenyl group. Phenyl
group, tolyl group, or naphthyl group are preferred in
consideration of economy. In particular, when the aryl group,
especially, phenyl group is introduced into component (A), the
compatibility with component (B) will be improved, and the weather
resistance of the obtained cured product will be improved. Examples
of the aralkyl group include benzyl group, phenetyl group, and
methyl phenyl methyl group. Examples also include groups in which
some or all of the hydrogen atoms bonded to the alkyl groups, aryl
groups, or the aralkyl groups are substituted by chlorine atoms,
brome atoms, or other halogen atoms. Examples of the alkoxy group
include methoxy group, ethoxy group, n-propoxy group, i-propoxy
group, n-butoxy group, sec-butoxy group, and tert-butoxy group.
R.sup.2 may be two or more types of the aforementioned groups.
In the formula, "a" represents the proportion of the C.sub.2-12
alkenyl groups with respect to the silicon atoms. It is a number
satisfying: 0<a<1, preferably, 0<a.ltoreq.0.6 or
0<a.ltoreq.0.4. In the formula, "b" represents the proportion of
the hydrogen atoms, C.sub.1-12 alkyl groups, C.sub.6-20 aryl
groups, C.sub.7-20 aralkyl groups, hydroxyl groups, or the
C.sub.1-6 alkoxy groups with respect to the silicon atoms. It is a
number satisfying: 0<b<3. However, the sum of "a" and "b" is
a number satisfying: 0.8<a+b<3, preferably,
1<a+b.ltoreq.2.2 or 1<a+b.ltoreq.2.0. If "a" is a number in
the aforementioned range, the curability of the obtained curable
organopolysiloxane composition at relatively low temperature is
good, and the mechanical strength of the obtained cured product is
good. While, when "b" is a number in the aforementioned range, the
mechanical strength of the obtained cured product is improved. On
the other hand, if the sum of "a" and "b" is a number in the
aforementioned range, the curability of the obtained curable
organopolysiloxane composition at relatively low temperature is
good, and the mechanical strength of the obtained cured product is
good.
There is no limitation on the molecular weight of component (A).
However, its weight average molecular weight measured using the gel
permeation chromatography method is preferred to be in the range of
1,000 to 50,000. If the weight average molecular weight of
component (A) is equal to or higher than the lower limit of the
aforementioned range, the mechanical property of the obtained cured
product is good. On the other hand, if the molecular weight is
equal to or lower than the upper limit of the aforementioned range,
the curing rate of the obtained curable organopolysiloxane
composition can be improved.
The organopolysiloxanes represented by the following average unit
formulas are listed as examples for component (A). These
organopolysiloxanes can be used either alone or as a mixture of two
or more kinds. In the formulas, Me, Ph, and Vi represent methyl
group, phenyl group, and vinyl group, respectively. x1, x2, x3, and
x4 are positive numbers, and the sum of x1, x2, x3, and x4 in a
molecule is 1.
(Me.sub.2ViSiO.sub.2).sub.x1(Me.sub.2SiO.sub.2/2).sub.x2
(Me.sub.3SiO.sub.1/2).sub.x1(Me.sub.2SiO.sub.2/2).sub.x2(MeViSiO.sub.2/2)-
.sub.x3
(Me.sub.2ViSiO.sub.1/2).sub.x1(Me.sub.2SiO.sub.2/2).sub.x2(MeViSiO.sub.2/-
2).sub.x3
(Me.sub.3SiO.sub.1/2).sub.x1(MeViSiO.sub.2/2).sub.x2(MeSiO.sub.3/2).sub.x-
3
(Me.sub.2ViSiO.sub.1/2).sub.x1(Me.sub.2SiO.sub.2/2).sub.x2(MeSiO.sub.3/2)-
.sub.x3
(Me.sub.2ViSiO.sub.1/2).sub.x1(Me.sub.2SiO.sub.2/2).sub.x2(MeViSiO.sub.2/-
2).sub.x3(MeSiO.sub.3/2).sub.x4
(Me.sub.2ViSiO.sub.1/2).sub.x1(Me.sub.2SiO.sub.2/2).sub.x2
(SiO.sub.4/2).sub.x3
(Me.sub.2ViSiO.sub.1/2).sub.x1(Me.sub.2SiO.sub.2/2).sub.x2(MePhSiO.sub.2/-
2).sub.x3
(Me.sub.3SiO.sub.1/2).sub.x1(MeViSiO.sub.2/2).sub.x2(MePhSiO.sub.2/2).sub-
.x3
(Me.sub.3SiO.sub.1/2).sub.x1(Me.sub.2SiO.sub.2/2).sub.x2(MeViSiO.sub.2/2)-
.sub.3(MePhSiO.sub.2/2).sub.x4
(Me.sub.2ViSiO.sub.1/2).sub.x1(MePhSiO.sub.2/2).sub.x2
(Me.sub.2PhSiO.sub.1/2).sub.x1(Me.sub.2SiO.sub.2/2).sub.x2(MeViSiO.sub.2/-
2).sub.x3
(MePh.sub.2SiO.sub.1/2).sub.x1(Me.sub.2SiO.sub.2/2).sub.x2(MeViSiO.sub.2/-
2).sub.x3
(Me.sub.2ViSiO.sub.1/2).sub.x1(Me.sub.2SiO.sub.2/2).sub.x2
(Ph.sub.2SiO.sub.2/2).sub.x3
(Me.sub.2ViSiO.sub.1/2).sub.x1(Me.sub.2SiO.sub.2/2).sub.x2
(PhSiO.sub.3/2).sub.x3
(Me.sub.3SiO.sub.1/2).sub.x1(MeViSiO.sub.2/2).sub.x2
(PhSiO.sub.3/2).sub.x3
(Me.sub.3SiO.sub.1/2).sub.x1(Me.sub.2SiO.sub.2/2).sub.x2(MeViSiO.sub.2/2)-
.sub.x3 (PhSiO.sub.3/2).sub.x4
(Me.sub.2ViSiO.sub.1/2).sub.x1(Me.sub.2SiO.sub.2/2).sub.x2(MePhSiO.sub.2/-
2).sub.x3 (PhSiO.sub.3/2).sub.x4
(Me.sub.2ViSiO.sub.1/2).sub.x1(Me.sub.2SiO.sub.2/2).sub.x2(MeSiO.sub.3/2)-
.sub.x3 (PhSiO.sub.3/2).sub.x4
The compound for component (B) is a component that reacts with the
alkenyl groups in component (A) to cure this composition. There is
no limitation on component (B) as long as it has at least two thiol
groups in a molecule. Preferably, it is
(B1) a thiol group-containing organopolysiloxane represented by the
following average compositional formula:
R.sup.3.sub.cR.sup.4.sub.dSiO.sub.(4c-d)/2 and/or (B2) a thiol
compound having at least two thiol groups in a molecule.
For component (B1), in the formula, R.sup.3 is at least one type of
thiol group selected from a group consisting of thiolalkyl groups
and thiolaryl groups. Examples of the thiolalkyl group include
3-thiolpropyl group, 4-thiolbutyl group, and 6-thiolhexyl group.
Examples of the thiolaryl group include 4-thiolphenyl group,
4-thiolmethylphenyl group, and 4-(2-thiolethyl)phenyl group.
Component (B1) has at least two thiol groups in a molecule.
In the formula, R.sup.4 represents a hydrogen atom, C.sub.1-12
alkyl group, C.sub.6-20 aryl group, C.sub.7-20 aralkyl group,
hydroxyl group, or a C.sub.1-6 alkoxy group. Examples of the alkyl
group are the same as those of said R.sup.2. Methyl group is
preferred in consideration of economy and heat resistance. Examples
of the aryl group are the same as those of said R.sup.2. Phenyl
group, tolyl group, or naphthyl group are preferred in
consideration of economy. Examples of the aralkyl group are the
same as those of said R.sup.2. Examples also include the groups in
which some or all of the hydrogen atoms bonded to the alkyl groups,
aryl groups, or the aralkyl groups are substituted by chlorine
atoms, brome atoms, or other halogen atoms. Examples of the alkoxy
group are the same as those of said R.sup.2. R.sup.4 may be two or
more types of the aforementioned groups.
In the formula, "c" represents the proportion of the thiol groups
with respect to the silicon atoms. It is a number satisfying:
0<c<1, preferably, 0<c.ltoreq.0.6 or 0<c.ltoreq.0.4.
Also, in the formula, "d" represents the proportion of the hydrogen
atoms, C.sub.1-12 alkyl groups, C.sub.6-20 aryl groups, C.sub.7-20
aralkyl groups, hydroxyl groups, or the C.sub.1-6 alkoxy groups
with respect to the silicon atoms. It is a number satisfying:
0<d<3. However, the sum of "c" and "d" is a number
satisfying: 0.8<c+d<3, preferably, 1<c+d.ltoreq.2.5 or
1<c+d.ltoreq.2.3. If "c" is a number in the aforementioned
range, the curability of the obtained curable organopolysiloxane
composition at relatively low temperature is good, and the
mechanical strength of the obtained cured product is good. While,
when "d" is a number in the aforementioned range, the mechanical
strength of the obtained cured product is improved. On the other
hand, if the sum of "c" and "d" is a number in the aforementioned
range, the curability of the obtained curable organopolysiloxane
composition at relatively low temperature is good, and the
mechanical strength of the obtained cured product is good.
There is no limitation on the molecular weight of component (B1).
However, its weight average molecular weight measured using the gel
permeation chromatography method is preferred to be in the range of
500 to 50,000. If the weight average molecular weight of component
(B1) is equal to or higher than the lower limit of the
aforementioned range, the mechanical property of the obtained cured
product is good. On the other hand, if the molecular weight is
equal to or lower than the upper limit of the aforementioned range,
the curing rate of the obtained curable organopolysiloxane
composition can be improved.
The organopolysiloxanes represented by the following average unit
formulas are listed as examples of component (B1). These
organopolysiloxanes can be used either alone or as a mixture of two
or more kinds. In the formulas, Me, Ph, and Thi represent methyl
group, phenyl group, and 3-thiolpropyl group, respectively. y1, y2,
y3, and y4 are positive numbers, and the sum of y1, y2, y3, and y4
in a molecule is 1.
(Me.sub.3SiO.sub.1/2).sub.y1(Me.sub.2SiO.sub.2/2).sub.y2(MeThiSiO.sub.2/2-
).sub.y3 (PhSiO.sub.3/2).sub.y4
(Me.sub.3SiO.sub.1/2).sub.y1(Me.sub.2SiO.sub.2/2).sub.y2(MeThiSiO.sub.2/2-
).sub.y3(MeSiO.sub.3/2).sub.y4
(Me.sub.3SiO.sub.1/2).sub.y1(MeThiSiO.sub.2/2).sub.y2
(PhSiO.sub.3/2).sub.y3
(Me.sub.3SiO.sub.1/2).sub.y1(MeThiSiO.sub.2/2).sub.y2(MeSiO.sub.3/2).sub.-
y3 (PhSiO.sub.3/2).sub.y4
(Me.sub.3SiO.sub.1/2).sub.y1(Me.sub.2SiO.sub.2/2).sub.y2(MeThiSiO.sub.2/2-
).sub.y3
(Me.sub.3SiO.sub.1/2).sub.y1(Me.sub.2SiO.sub.2/2).sub.y2(MePhSiO.sub.2/2)-
.sub.y3(MeThiSiO.sub.2/2).sub.y4
(Me.sub.3SiO.sub.1/2).sub.y1(MePhSiO.sub.2/2).sub.y2(MeThiSiO.sub.2/2).su-
b.y3
(Me.sub.3SiO.sub.1/2).sub.y1
(Ph.sub.2SiO.sub.2/2).sub.y2(MeThiSiO.sub.2/2).sub.y3
(Me.sub.2SiO.sub.2/2).sub.y1(MeThiSiO.sub.2/2).sub.y2
(PhSiO.sub.3/2).sub.y3
(Me.sub.2SiO.sub.2/2).sub.y1 (ThiSiO.sub.3/2).sub.y2
(Me.sub.3SiO.sub.1/2).sub.y1(Me.sub.2SiO.sub.2/2).sub.2
(ThiSiO.sub.3/2).sub.y3
(Me.sub.3SiO.sub.1/2).sub.y1(Me.sub.2SiO.sub.2/2).sub.y2
(ThiSiO.sub.3/2).sub.y3(MeSiO.sub.3/2).sub.y4
(Me.sub.3SiO.sub.1/2).sub.y1(Me.sub.2SiO.sub.2/2).sub.y2
(ThiSiO.sub.3/2).sub.y3 (PhSiO.sub.3/2).sub.y4
(Me.sub.3SiO.sub.1/2).sub.y1
(ThiSiO.sub.3/2).sub.y2(MeSiO.sub.3/2).sub.y3
(Me.sub.3SiO.sub.1/2).sub.y1 (ThiSiO.sub.3/2).sub.y2
(PhSiO.sub.3/2).sub.y3
(Me.sub.3SiO.sub.1/2).sub.y1 (ThiSiO.sub.3/2).sub.y2
(Me.sub.3SiO.sub.1/2).sub.y1(Me.sub.2SiO.sub.2/2).sub.y2(MeThiSiO.sub.2/2-
).sub.y3 (SiO.sub.4/2).sub.y4
(Me.sub.3SiO.sub.1/2).sub.y1(MeThiSiO.sub.2/2).sub.y2
(SiO.sub.4/2).sub.y3
(Me.sub.3SiO.sub.1/2).sub.y1(Me.sub.2SiO.sub.2/2).sub.y2
(ThiSiO.sub.3/2).sub.y3 (SiO.sub.4/2).sub.y4
There is no limitation on the thiol compound for (B2) as long as it
has at least two thiol groups in a molecule. Specific examples
include trimethylolpropane-tris(3-thiolpropionate),
trimethylolpropane-tris(3-thiolbutylate),
trimethylolethane-tris(3-thiolbutylate),
pentaerythritol-tetrakis(3-thiolpropionate), tetraethylene
glycol-bis(3-thiolpropionate),
dipentaerythritol-hexakis(3-thiolpropionate),
pentaerythritol-tetrakis(3-thiolbutylate),
1,4-bis(3-thiolbutylyloxy)butane, and other ester compounds of
thiol carboxylic acids and polyhydric alcohols; ethanedithiol,
propanedithiol, hex-anemethylenedithiol, decamethylenedithiol,
bis(2-thiolethyl)ether, 3,6-dioxa-1,8-octanedithiol,
1,4-benzenedithiol, toluene-3,4-dithol, xylylenedithol, and other
aliphatic or aromatic thiol compounds; and
1,3,5-tris[(3-thiolpropionyloxy)-ethyl]-isocyanurate,
1,3,5-tris[(3-thiolbutylyloxy)-ethyl]-isocyanurate, and mixtures of
two or more kinds of the aforementioned compounds.
There is limitation on the molecular weight of the thiol compound,
which is preferred to be in the range of 200 to 2,000, 300 to
1,500, or 400 to 1,500. If the molecular weight is equal to or
higher than the the lower limit of the aforementioned range, the
volatility of the thiol compound becomes low so that the problem of
offensive odor can be alleviated. On the other hand, if the
molecular weight is equal to or lower than the upper limit of the
aforementioned range, the solubility with respect to component (A)
can be improved.
The content of component (B) in this composition is such that the
amount of the thiol groups in this component is in the range of 0.3
to 3 mol, preferably, in the range of 0.5 to 2 mol, or 0.8 to 1.5
mol with respect to 1 mol of the alkenyl groups in component (A).
If the content of component (B) is equal to or higher than the
lower limit of the aforementioned range, the obtained curable
organopolysiloxane composition can be well cured. On the other
hand, if the content is equal to or lower than the upper limit of
the aforementioned range, the mechanical strength of the obtained
cured product can be improved.
Component (C) is a component used for accelerating curing of this
composition. It is an azo compound and/or an organic peroxide.
Examples of the azo compound include
1,1'-azobis(cyclohexane-1-carbonitrile),
2,2'-azobis(2-methylbutylonitrile), 2,2'-azobis(isobutylonitrile)
(AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile),
2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), and other
azonitrile compounds; dimethyl-2,2'-azobis(isobutylate), and other
azoester compounds; 2,2'-azobis(N-butyl-2-methylpropionamide),
2,2'-azobis[N-(2-propenyl)-2-methylpropionamide],
2,2'-azobis[N-(2-(hydroxyethyl)-2-methylpropionamide), and other
azoamide compounds.
Examples of the organic peroxide include dibenzoyl peroxide,
bis(3-carboxypropionyl)peroxide, dilauroyl peroxide,
di(3,5,5-trimethylhexanoyl) peroxide, diisobutylyl peroxide, and
other diacyl peroxide compounds; di(n-propylperoxy)dicarbonate,
di(isopropylperoxy)dicarboante, di(2-ethylhexylperoxy)dicarboante,
and other peroxydicarbonate compounds;
tert-butylperoxy-2-ethylhexanoate,
tert-hexylperoxy-2-ethylhexanoate,
1,1,3,3-tetramethylbutylperoxy-oxy-2-ethylhexanoate,
tert-butylperoxypivalate, tert-butylperoxyneodecanate,
1,1,3,3-tetramethylbutylperoxyneodecanate, cumylperoxy-neodecanate,
and other peroxyester compounds;
1,1'-di(tert-butylperoxy)-2-methylcyclohexane,
1,1'-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, and other
peroxyketal compounds.
It is preferred to use an azo compound as component (C). These azo
compounds can be used either alone or as a mixture of two or more
kinds. Also, it is preferred to use a compound with a 10 hrs.
half-life temperature of 25.degree. C. or higher but lower than
70.degree. C. as component (C). The curing rate and bathlife of the
curable organopolysiloxane composition disclosed in the present
invention can be adjusted by appropriately selecting component
(C).
The content of component (C) preferred to be in the range of 0.01
to 10 mass %, more preferably, in the range of 0.01 to 1 mass % or
0.05 to 0.5 mass % with respect to the total amount of components
(A) to (C). If the content of component (C) is equal to or higher
than the lower limit of the aforementioned range, the curing
reaction of the obtained composition can be accelerated. On the
other hand, if the content equal to equal to or lower than the
upper limit of the aforementioned range, the obtained cured product
is difficult to color even by heat aging. The curing rate and
bathlife of this composition can be adjusted by appropriately
adjusting the content of component (C) in this composition.
Component (D) is a component used for improving the storage
stability of this composition. It is one or more types of compounds
selected from a group consisting of quinone compounds, compounds
having one or two aromatic hydroxyl groups in one molecule,
compounds having one thiol group in a molecule, nitrosamine
compounds, hydroxylamine compounds, and phenothiazine
compounds.
Examples of the quinone compound include 1,4-benzoquinone
(p-quinone), methyl-p-benzoquinone, 2,5-dimethyl-1,4-benzoquinone,
1,4-naphthoquinone, 2,3-dichloro-1,4-naphthoquinone, anthraquinone,
2-methylanthraquinone, 2-ethylanthraquinone, 2-aminoanthraquinone,
1-aminoanthraquinone, 1-amino-2-methylanthraquinone,
2-amino-3-hydroxyanthraquinone, 1,4-dihydroxyanthraquinone,
1,5-dihydroxyanthraquinone, 1,8-dihyroxyanthraquinone,
1-chloroanthraquinone, 1,4-diaminoanthraquinone,
1,5-dichloroanthraquinone, 1,8-dichloroanthraquinone, and
1-nitroanthraquinone.
Examples of the compound having one or two aromatic hydroxyl groups
in a molecule include hydroquinone, tert-butylhydroquinone,
methylhydroquinone, phenyl-hydroquinone, chlorohydroquinone,
2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone,
trimethylhydroquinone, methoxyhydroquinone, and other hydroquinone
compounds; 4-tert-butylcatechol and other catechol compounds;
4-ethoxyphenol, 4-methoxyphenol, 4-propoxyphenol,
2,6-bis(hydroxymethyl)-p-cresol, 2,6-di-tert-butyl-4-methylphenol,
2,6-di-tert-butyl-4-hydroxymethylphenol,
2-(4-hydroxyphenyl)ethanol, 4-nitrosophenol, and other substituted
phenol compounds.
Examples of the compound having one thiol group in a molecule
include benzenethiol, 2-ethylbenzenethiol, 4-ethylbenzenethiol,
4-isopropylbenzenethiol, 4-tert-butylbenzenethiol,
3-methoxybenzenethiol, 5-tert-butyl-2-methylbenzenethiol,
3-chlorobenzenethiol, 4-chlorobenzenethiol,
2,4-dichlorobenzenethiol, and other aromatic thiol compounds;
benzyl mercaptan, 4-chlorobenzyl mercaptan, 1-butanethiol,
2-butanethiol, 2-methyl-1-propanethiol, 2-methyl-2-propanethiol,
cyclo-hexanethiol, 1-hexanethiol, 2-ethyl-1-hexanethiol,
1-decanethiol, 1-dodecanethiol, and other aliphatic thiol
compounds; 2-benzimidazolethiol, 2-benzoxazolthiol,
2-pyridinethiol, 4,6-dimethyl-2-thiolpyrimidine,
2-thiazoline-2-thiol, and other heterocyclic thiol compounds.
Examples of the nitrosoamine compound include
N-ethyl-N-(4-hydroxybutyl)nitrosamine,
N-butyl-N-(4-hydroxybutyl)nitrosamine, ammonium nitrosophenyl
hydroxylamine (Cupferron), N,N'-dinitrosopentamethylene tetramine,
N-nitrosodibutylamine, N-nitrosodiphenylamine,
N-nitroso-N-methylaniline, N-methyl-N-nitrosurethane, and other
non-metallic compounds; N-nitrosophenylhyroxylamine aluminum salts,
and other metal salt compounds.
Examples of the hydroxylamine compound include
N-benzoyl-N-phenylhydroxylamine, N,N-diethylhydroxylamine,
N,N-dibenzylhydroxylamine, and N,N-dioctadecylhydroxylamine.
Examples of the phenothiazine compound include phenothiazine,
2-chlorophenothiazine, 2-methoxyphenothiazine,
2-methylthiophenothiazine, and 2-ethylthiophenothiazine.
The content of component (D) is preferred to be in the range of
0.001 to 10 mass %, more preferably, in the range of 0.005 to 5
mass % or 0.005 to 1 mass % with respect to the total amount of
components (A) to (D). If the content of component (D) is equal to
or higher than the lower limit of the aforementioned range, the
storage stability of the obtained composition can be improved. If
the content is equal to or lower than the upper limit of the
aforementioned range, the curing rate is sufficiently high during
thermosetting, and the obtained cured compound is difficult to
color even due to heat aging. The curing rate and bathlife of this
composition can be adjusted by appropriately adjusting the content
of component (D).
The composition of the present invention can be used without using
solvent. However, if it is desired to lower the viscosity of this
composition or form a cured product on a thin film, (E) an organic
solvent can be added as demanded. There is no special limitation on
the organic solvent as long as it does not hinder curing of this
composition and can homogenously dissolve the entire composition.
It is preferred to use an organic solvent with a boiling point of
70.degree. C. or higher but lower than 200.degree. C. Specific
examples include i-propyl alcohol, t-butyl alcohol, cyclohexanol,
ethyl acetate, propyl acetate, butyl acetate, cyclohexanone, methyl
ethyl ketone, methyl isobutyl ketone, toluene, xylene, mesitylene,
1,4-dioxane, dibutyl ether, anisole, 4-methyl anisole, ethyl
benzene, ethoxybenzene, ethylene glycol, ethylene glycol dimethyl
ether, ethylene glycol diethyl ether, 2-methoxyethanol (ethylene
glycol monomethyl ether), diethylene glycol dimethyl ether,
diethylene glycol monomethyl ether, 1-methoxy-2-propyl acetate,
1-ethoxy-2-propylacetate, octamethyl cyclotetrasiloxane, hexamethyl
disiloxane, and other non-halogen solvents: 1,1,2-trichloroethane,
chlorobenzene, and other halogen-based solvents; mixtures of two or
more types of the aforementioned solvents.
There is no limitation on the content of component (E) in this
composition. Preferably, it is 3,000 parts by mass or less, or
1,000 parts by mass or less with respect to 100 parts by weight of
the total amounts of components (A) to (C).
There is no limitation on the viscosity of this composition at
25.degree. C., which is preferred to be in the range of 10 to
100,000 mPas or in the range of 10 to 10,000 mPas. It is also
possible to add an organic solvent into this composition to adjust
the viscosity to the aforementioned range.
If necessary, other components can also be added into the
composition of the present invention as long as they do not affect
the objective of the present invention. Examples of these
components include fumed silica, crystalline silica, fused silica,
wet silica, titanium oxide, zinc oxide, iron oxide, and other metal
oxide fine powders; vinyltri-ethoxysialne, allyltrimethoxysilane,
allyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane,
3-methacryloxypropyltrimethoxysilane, and other adhesion promoters;
nitrides, sulfides, and other inorganic fillers, pigments, heat
resistance improving agents, and other well-known additives.
The composition of the present invention can be prepared by
homogeneously blending components (A) to (D) and any other
components as demanded. Various types of stirrers or kneaders can
be used to mix the components at ordinary temperature when
preparing the composition of the present invention. If it is a
composition that is not easy to cure during blending, it is also
possible to perform blending under heating. There is no limitation
on the order of adding the components, which can be blended in any
order.
The curing reaction of this composition can be carried out even at
a relatively low temperature of 70 to 80.degree. C. The time taken
by the curing reaction varies depending on the types of components
(A) to (D) and the shape of the molding product but is usually
within 1 hr. The time needed to cure a thin film-like composition
with a thickness of 0.1 mm or less is usually within 5 min.
This composition can be applied to coating on a base material
lacking heat resistance since it can be cured even at a relatively
low temperature. Examples of the coating method used for this
composition include gravure coating, offset coating, offset
gravure, roll coating, reverse roll coating, air knife coating,
curtain coating, and comma coating. Examples of the base material
include paperboard, corrugated paper, clay-coated paper, polyolefin
laminated paper, particularly, polyethylene laminated paper,
synthetic resin film/sheet/coating film, natural fiber fabric,
synthetic fiber fabric, artificial leather cloth, metal foil, metal
sheet, and concrete. Synthetic resin film/sheet/coating film is
particularly preferred. In the case of a multi-layer coating film,
this composition is usually coated on a coating film made of epoxy
resin, acrylic resin, urethane-based resin, or the like.
In the following, the cured product of the present invention will
be described in details.
The cured product of the present invention is characterized by
being obtained by curing the aforementioned curable
organopolysiloxane composition. There is no special limitation on
the shape of the cured product, which may be sheet, film, tape, or
the like.
For example, after the composition of the present invention is
coated on a film-like base material, a tape-like base material, or
a sheet-like base material, it is cured at 70 to 80.degree. C. A
cured film comprising this cured product can be formed on the
surface of the aforementioned base material. There is no limitation
on the thickness of the cured film, which is preferred to be in the
range of 0.1 to 500 m, more preferably, in the range of 0.1 to 50
m.
EXAMPLES
The curable organopolysiloxane composition and its cured product
disclosed in the present invention will be described in details
based on Examples. In formulas, Me, Ph, Vi, and Thi represent
methyl group, phenyl group, vinyl group, and 3-thiolpropyl group,
respectively. The viscosity, weight average molecular weight, and
thiol equivalent in the Examples were measured as follows.
<Viscosity>
The viscosity at 25.degree. C. was measured using a rotary
viscometer VG-DA produced by Shibaura System Co., Ltd.
<Weight Average Molecular Weight>
The weight average molecular weight relative to standard
polystyrene was derived by a gel permeation chromatography using an
RI detector.
<Vinyl Equivalent, Thiol Equivalent>
The vinyl equivalent (g/mol) or thiol equivalent (g/mol) of the
organopolysiloxane was derived from a structure identified by
nuclear magnetic resonance spectral analysis.
Synthesis Example 1: Preparation of a Vinyl Group-Containing
Organopolysiloxane
99 g of phenyltrimethoxysilane, 1200 g of dimethyldimethoxysilane,
466 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, and 0.9 g of
trifluoromethanesulfonic acid were added and stirred in a reactor
equipped with stirrer, thermometer, refluxcondenser, and dropping
funnel. 315 g of ion exchange water was added dropwise at room
temperature, followed by 1 h of stirring performed under methanol
reflux. After cooling, toluene was added, and 7.5 g of a
11N-potassium hydroxide aqueous solution was added. The generated
methanol and the unreacted water were removed by azeotropic
dehydration. After the system was neutralized by using 7.3 g of
acetic acid, the remaining low-boiling fractions were removed by
distillation performed under a reduced pressure. Then, the solid
by-product was filtered out, thereby obtaining a colorless
transparent liquid with a viscosity of 52 mPas.
This liquid had weight average molecular weight=1,200 and vinyl
equivalent=371 g/mol. The .sup.13C-nuclear magnetic resonance
spectral analysis confirmed that this liquid was a vinyl
group-containing organopolysiloxane represented by the following
average unit formula:
(ViMe.sub.2SiO.sub.1/2).sub.0.25(Me.sub.2SiO.sub.2/2).sub.0.50(PhSiO.sub.-
3/2).sub.0.25 and the following average compositional formula:
Vi.sub.0.25Ph.sub.0.25Me.sub.1.50SiO.sub.1.00 The content of
hydroxyl groups or methoxy groups was less than 1 wt %.
Synthesis Example 2: Preparation of a thiol group-containing
organopolysiloxane
1,374 g of 3-thiolpropyltrimethoxysilane, 1,680 g of
dimethyldimethoxysilane, and 1.18 g of trifluoromethanesulfonic
acid were added and stirred in a reactor equipped with stirrer,
thermometer, refluxcondenser, and dropping funnel. 882 g of ion
exchange water was added dropwise at room temperature, followed by
1 hr. of stirring performed under methanol reflux. After cooling,
calcium carbonate and cyclohexane were added. The generated
methanol and the unreacted water were removed by azeotropic
dehydration. The remaining low-boiling fractions were removed by
distillation performed under a reduced pressure. Then, the solid
by-product was filtered out, thereby obtaining a colorless
transparent liquid with a viscosity of 560 mPas.
This liquid had weight average molecular weight=4,000 and thiol
equivalent=260 g/mol. The .sup.13C-nuclear magnetic resonance
spectral analysis confirmed that this liquid was a thiol
group-containing organopolysiloxane represented by the following
average unit formula:
(Me.sub.2SiO.sub.2/2).sub.0.65(ThiSiO.sub.3/2).sub.0.35 and the
following average compositional formula:
Thi.sub.0.35Me.sub.1.30SiO.sub.1.18
Practical Examples 1 to 15, Comparative Examples 1 to 5
The following components were used to prepare solventless curable
organopolysiloxane compositions (parts by mass) shown in Tables 1
to 3. For these curable organopolysiloxane compositions, the amount
of the thiol groups in component (B) was adjusted to 1 mol with
respect to 1 mol of the vinyl groups in component (A).
The following component was used as component (A).
(a-1): The vinyl group-containing organopolysiloxane prepared in
Synthesis Example 1
The following component was used as component (B).
(b-1): The thiol group-containing organopolysiloxane prepared in
Synthesis Example 2
The following components were used as component (C).
(c-1): 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile)
(c-2): 2,2'-azobis(2,4-dimethylvaleronitrile)
(c-3): 2,2'-azobis(2-methylbutylonitrile)
(c-4): Dibenzoylperoxide
(c-5): 2,2'-dimethoxy-2-phenylacetophenone
(c-6): 2-hydroxy-2-methylpropiophenone
The following components were used as component (D).
(d-1): Naphthoquinone
(d-2): Benzoquinone
(d-3): 2,6-di-tert-butyl-4-methylphenol
(d-4): 4-methoxyphenol
(d-5): 1-dodecanethiol
(d-6): N-nitrosophenylhydroxylamine aluminum salt
(d-7): N,N-diethylhydroxylamine
(d-8): Phenothiazine
The curable organopolysiloxane compositions were evaluated as
follows.
<Appearance>
After each curable organopolysiloxane composition was prepared, its
appearance was visually observed.
<Curability>
The curable organopolysiloxane composition was spread on an
aluminum dish in such an amount that the thickness of the cured
product would be 100 to 200 m. The dish was loaded into an oven
kept at 80.degree. C. The curing time (the time taken until the
composition was not stuck to fingers: gelling time) was derived,
and the curability was evaluated based on the following
standards.
: The gelling time at 80.degree. C. is within 10 min.
: The gelling time at 80.degree. C. is longer than 10 min but
within 30 min.
.DELTA.: The gelling time at 80.degree. C. is longer than 30 min
but within 1 hr.
X: Not cured at 80.degree. C. in 1 hr.
The same amount of the curable organopolysiloxane composition was
spread on an aluminum dish in the same way as described above, and
the curability at 25.degree. C. was evaluated based on the
following standards.
: Not cured at 25.degree. C. in 48 hrs.
: The gelling time at 25.degree. C. is longer than 24 hrs. but
within 48 hrs.
X: The gelling time at 25.degree. C. is within 24 hrs.
TABLE-US-00001 Practical Examples 1 2 3 4 Components of component
(a-1) 100 100 100 100 the Curable component (b-1) 71.7 71.7 71.7
71.7 Organopolysiloxane component (c-1) 0.17 0.85 0.17 0.034
Compositions component (c-2) -- -- -- -- (parts by mass) component
(c-3) -- -- -- -- component (c-4) -- -- -- -- component (c-5) -- --
-- -- component (c-6) -- -- -- -- component (d-1) 0.085 0.085 0.017
0.0017 component (d-2) -- -- -- -- component (d-3) -- -- -- --
component (d-4) -- -- -- -- component (d-5) -- -- -- -- component
(d-6) -- -- -- -- component (d-7) -- -- -- -- component (d-8) -- --
-- -- Content of component 0.1 0.5 0.1 0.02 (C) (mass %) Content of
component 0.05 0.05 0.01 0.001 (D) (mass %) Appearance Yellowish
Yellowish Light green Light green green and green and and and
transparent transparent transparent transparent Curability at
80.degree. C. Curability at 25.degree. C. Comparative Examples 1 2
3 4 5 Components of component (a-1) 100 100 100 100 100 the Curable
component (b-1) 71.7 71.7 71.7 71.7 71.7 Organopolysiloxane
component (c-1) 0.034 -- -- -- -- Compositions component (c-2) --
-- -- -- -- (parts by mass) component (c-3) -- -- -- -- --
component (c-4) -- -- -- -- -- component (c-5) -- -- 0.085 -- --
component (c-6) -- -- -- 0.85 -- component (d-1) -- -- 0.085 0.085
-- component (d-2) -- -- -- -- -- component (d-3) -- -- -- -- --
component (d-4) -- -- -- -- -- component (d-5) -- -- -- -- 0.0017
component (d-6) -- -- -- -- -- component (d-7) -- -- -- -- --
component (d-8) -- -- -- -- -- Content of component 0.02 0 0.5 0.5
0 (C) (mass %) Content of component 0 0 0.05 0.05 0.001 (D) (mass
%) Appearance Colorless Colorless Yellow Yellow Yellow and and and
and and transparent transparent transparent transparent transparent
Curability at 80.degree. C. X X X X Curability at 25.degree. C.
X
TABLE-US-00002 Practical Examples 5 6 7 8 9 Components of component
(a-1) 100 100 100 100 100 the Curable component (b-1) 71.7 71.7
71.7 71.7 71.7 Organopolysiloxane component (c-1) -- -- -- -- 0.017
Compositions component (c-2) 0.085 0.85 -- -- -- (parts by mass)
component (c-3) -- -- 17.17 -- -- component (c-4) -- -- -- 1.7 --
component (c-5) -- -- -- -- -- component (c-6) -- -- -- -- --
component (d-1) -- 0.085 0.17 0.085 -- component (d-2) -- -- -- --
-- component (d-3) -- -- -- -- -- component (d-4) -- -- -- -- --
component (d-5) 17.17 -- -- -- 0.0017 component (d-6) -- -- -- --
-- component (d-7) -- -- -- -- -- component (d-8) -- -- -- -- --
Content of component 0.05 0.5 10 0.02 0.01 (C) (mass %) Content of
component 10.0 0.05 0.1 0.001 0.001 (D) (mass %) Appearance
Colorless Colorless Colorless Colorless Colorless and and and and
and transparent transparent transparent transparent transparent
Curability at 80.degree. C. .DELTA. Curability at 25.degree. C.
TABLE-US-00003 TABLE 3 Practical Examples 10 11 12 Components
component (a-1) 100 100 100 of the Curable component (b-1) 71.7
71.7 71.7 Organopolysiloxane component (c-1) 0.017 0.17 0.17
Compositions component (c-2) -- -- -- (parts by mass) component
(c-3) -- -- -- component (c-4) -- -- -- component (c-5) -- -- --
component (c-6) -- -- -- component (d-1) -- -- -- component (d-2)
0.0085 -- -- component (d-3) -- 0.017 -- component (d-4) -- --
0.017 component (d-5) -- -- -- component (d-6) -- -- -- component
(d-7) -- -- -- component (d-8) -- -- -- Content of component (C)
(mass %) 0.1 0.1 0.1 Content of component (D) (mass %) 0.005 0.01
0.01 Appearance Light Colorless Colorless green and and and
transparent transparent transparent Curability at 80.degree. C.
Curability at 25.degree. C. 13 14 15 Components component (a-1) 100
100 100 of the Curable component (b-1) 71.7 71.7 71.7
Organopolysiloxane component (c-1) 0.017 0.017 0.017 Compositions
component (c-2) -- -- -- (parts by mass) component (c-3) -- -- --
component (c-4) -- -- -- component (c-5) -- -- -- component (c-6)
-- -- -- component (d-1) -- -- -- component (d-2) -- -- --
component (d-3) -- -- -- component (d-4) -- -- -- component (d-5)
-- -- -- component (d-6) 0.0085 -- -- component (d-7) -- 0.017 --
component (d-8) -- -- 0.017 Content of component (C) (mass %) 0.1
0.1 0.1 Content of component (D) (mass %) 0.005 0.01 0.01
Appearance Colorless Colorless Colorless and and and transparent
transparent transparent Curability at 80.degree. C. Curability at
25.degree. C.
It was confirmed based on the results of Practical Examples 1 to 4
that the curable organopolysiloxane composition of the present
invention could be cured quickly at 80.degree. C. and had
sufficiently long uncured time at 25.degree. C. It was also
confirmed that the curability at these temperatures could be
adjusted by optimizing the dosages of components (C) and (D).
On the other hand, it was confirmed based on the results of
Comparative Examples 1 and 2 that the curable organopolysiloxane
composition containing no component (D) and the curable
organopolysiloxane composition containing neither component (C) nor
component (D) could satisfy the curability at these two
temperatures at the same time.
It was confirmed based on the results of Comparative Examples 3 and
4 that the curable organopolysiloxane composition using a photo
radical initiator was cured slowly at 80.degree. C.
It was confirmed based on the results of Practical Examples 5 to 9
that a curable organopolysiloxane composition that could be cured
quickly at 80.degree. C. and had sufficiently long uncured time at
25.degree. C. could be prepared by optimizing the dosages of
various components (C) and (D) in the curable organopolysiloxane
composition of the present invention.
On the other hand, it was confirmed based on the result of
Comparative Example 5 that the curability at 80.degree. C. of the
curable organopolysiloxane composition containing no component (C)
was insufficient.
It was confirmed based on the results of Practical Examples 10 to
15 that a wide range of components (D) could be applied to the
curable organopolysiloxane composition of the present invention and
a curable organopolysiloxane composition that could be cured
quickly at 80.degree. C. and had sufficiently long uncured time at
25.degree. C. could be prepared by optimizing the dosage of this
component.
INDUSTRIAL APPLICABILITY
Since the curable organopolysiloxane composition of the present
invention has good curability even at 80.degree. C., it can be used
for coating on an object to be coated lacking heat resistance, such
as plastic films.
* * * * *
References